Recovery and conversion of olefinic hydrocarbons



Jam.l 19, 1943.

E. G. BORDEN RECOVERY AND CONVERSION OF OLEFINIC HYDROCARBONS Filed April 28, 1939 2 Sheets-Sheet 1 RECT/FY/NG COLUMNS Jan. 19, 1943. E. G. BORDEN 2,308,856

RECOVERY AND CONVERSION OF OLEFINIC HYDROCARBONS CONVERSION F OLEFINIC` REcovERYANn HYDROCARBONS Edmund G. Borden, Little Neck, N. Y., assignor to Cities Service Oil Company,

New York, N. Y.,

a corporation of Pennsylvania Application April 28, 1939, Serial No. 270,556

Claims.

This invention relates to a continuous process for recovering unsaturated olefin hydrocarbon gases from normally gaseous mixtures containing substantial proportions of saturated or parafiin hydrocarbons and the conversion of the oleiins into other products.

This application is a continuation-impart of application Serial No. 84,790, filed June 12, 1936, for "Process for recovering olefin hydrocarbons.

Enormous quantities of olen hydrocarbons are available in such mixtures as the gases produced in the cracking of hydrocarbon oils, in the coking of coal, shales and other carbonaceous materials and in the polymerization of natural and other hydrocarbon gases. However, the olenns contained in these materials are mixed with substantial proportions of paraiiinic, cyclic and naphthenic hydrocarbons and hydrogen which are not suitable for use in the various manufacturing processes in which oleiins are particularly desirable. For example, in the manufacture of high anti-knock gasoline from the polymex-ization of olens, considerable diiilculty is encountered because the olens available in the mixtures of the type referred to above have too wide a range of characteristics and are mixed with too much paramn, acetylene and naphthenic hydrocarbon material of similar boiling point. In polymerization processes a high percentage of hydrogen is very undesirable because it severely limits the percentage of conversion or polymerization of the unsaturated hydrocarbons, particularly the oleiins. It is desirable, therefore, to have the gases substantially free of hydrogen. 'I'he presence of methane is also undesirable and tends to limit the percentage of conversion by polymerization of the oleiinic hydrocarbons.

Individual oleilns or relatively narrow fractions of oleiins which are relatively free from saturated hydrocarbons are highly desirable for many other processes, particularly for the manufacture of organic compounds, such as alcohols, esters, etc.

The primary object therefore of the present invention is to provide a continuous process for the selective separation of olefin hydrocarbons from gaseous mixtures of the type referred to above, the fractionation of the resulting separated oletlns into selected narrow fractions or separate individual compounds, and the treatment of these unsaturated hydrocarbons to manufacture chemical compounds or to polymerize them for the manufacture of motor fuels.

Another object of the invention is to provide a continuous process for the separation of indiv vidual or groups of hydrocarbon compounds from hydrocarbon gases, the absorption of the oleilns in chemically reacting agents or the polymerization of the olefins under heat and pressure or with a catalyst, and the recirculation of unreacted oleiins back through the process with additional olen in carrying out the desired reactions.

A further object of the invention is the provision of a, continuous process for extracting olens from gaseous mixtures of the type referred to above by the use of selective solvents. such for example as the higher aliphatic ethers, butyl ether, amyl ether and similar compounds as well as their chlorinated products.

Accordingly, the continuous process of the present invention comprises the steps of passing cracking still gases, for example, through one or more absorption towers in countercurrent contact with a selectivesolvent for olens such as isoamyl ether, the discharge of the unabsorbed parailinic gases and hydrogen from the top of the absorber, the passage of the solvent charged with oleflns from the bottom of the absorber, removal from the latter of the absorbed olens, and the separation of various individual oleiins or narrow fractions in accordance with their boiling points. The latter operations may be effectively carried out by passing the solvent and dissolved olens into a still, vaporizing the dissolved oleiins and passing them through a series of high pressure fractionatlng towers, from each of which a selected fraction is taken overhead.

'Ihe selective solvents preferably employed in accordance with the features of the present invention comprise the aliphatic ethers containing four or more carbon atoms to the molecule, of the type of isoamyl ether and the butyl ethers as well as the halogenated products of these ethers, particularly the dichlor products. Isoamyl ether for example, is a particularly eilicient extracting agent. Other examples of this class of solvents are, dichlorisobutyl ether and dichlorisoamyl ether.

Other features and objects of the continuous process of the present invention will be apparent to those skilled in the art, from the following more detailed description thereof, taken in connection with the accompanying drawings in which:

Fig. l is a diagrammatic showing of an assembly of apparatus elements particularly adapted for carrying out the improved process.

Fig. 2 is a diagrammatic showing of a modinewA oli-HCE;

ture of from 20 C. to 25 C., depending upon the solvent and the type of gases to be extracted. The drier the gases, that is, the lower the boiling point of the constituents of the gas, the lower the temperature of the solvent should be. in order to provide for the heat of absorption of the oleilns.

In the absorber 8 the solvent passes downwardly over a series of bubble trays countercurrent to the gases being treated which are introduced under pressure Ithrough a valved line 8. The pressure maintained in the absorber l may vary from 50 to 300 lbs. per square inch, the higher pressures being used for the treatment of the relatively drier gases. As the solvent pass downwardly .through the absorber it selectively absorbs or dissolves the oleiins from the gaseous mixture without taking up any substantial proportion of the paratlln hydrocarbons and hydrogen contained in the gases. The unabsorbed parafilns and hydrogen which may contain traces of undissolved oleiins a-re discharged from the absorber 6 through a valved line i..

In cases where the gas being treated contains a comparatively large amount of gaseous products, such as methane, ethane, hydrogen, nitrogen and carbon dioxide, it may be desirable to separate gases such as methane, hydrogen, carbon dioxide and nitrogen by passing the gas.

through an absorber (not shown) in contact with an cil absorbing menstruum such as a gasoline, kerosene or neutral oil. This oil absorption will take out practically all-of the hydrocarbons both saturated and unsaturated allowing the hydrogen, nitrogen and carbon dioxide to pass on and by careful control of pressures and temperatures the methane can thus be selectively separated. The mixture then containing the saturated and unsaturated hydrocarbons, after release from the oil menstruum, -is treated in accordance with the present invention in order to selectively separate the olefinic hydrocarbons from the remaining hydrocarbons in the gas.

The solvent reaching the bottom of the absorber l l and which is substantially saturated with olens, is withdrawn through a line I2 and forced by means of -a pump mounted therein' through a heat exchanger I4, and discharged into a still I6. The pressure in the still Il may be maintained somewhat in excess of that used in the absorber i in order to provide a suitably high superatmospheric pressure in subsequent portions of the apparatus. This still is provided with a dephlegmator Il 'which serves to eliminate from the olen vapors driven ci! in the stili any proportion of the solvent which may be vaporized or occluded. The still I6 is also provided with a series of overiiow bailles so that the solvent, heated to successively higher temperatures as it passes through the still, will contain gradually decreasing proportions of olefin hydrocarbons. The stripped solvent is discharged from the still I6 through a valved line 2l and paed through heat exchanger I4 and then into line 2 by which it is conducted back to the absorption or extraction operation carried out in the absox-ber B.

The olehn vapors evolved in the still ii, may, in a particular instance, such as in the treatment of cracking still gases, contain ethylene, propylene, the butylenes andsome amylenes. This mixture of olenns is conducted from the still Il through a vapor line 22 and introduced into a nrst column 24 of a series of rectifying columns, in which the mixture is fractionated under high" pressure for the purpose of separating out the ethylene from the remaining constituents. In the various notifying columns the mixtures are fractionated in accordance with the boiling point of the -desired overhead products, which may correspond to the boiling points of the individual oleiins or to certain classes of oleiins, such for example, as the butylenes.

The temperature gradient in the rectiiying column 24 is controlled in relation to the pressure maintained therein (by providing a suitable heating coil in the base of the column) so that ethylene is discharged as a gas or vapor through a vapor line 2l, condensed by refrigeration in a condenser 2l, and passed into a line 30 from which the condensate may be sent to a receiver, or, as hereinafter described, .to a polymerization zone. Instead of condensing .the ethylene discharged through the line 26, it may be used directly in gas or vapor form in any manufacturing process such as a polymerization operation carried out at high temperature and pressure for the manufacture of anti-knock gasolines and aromatic hydrocarbons. When' the ethylene is condensed, any portion of the condensate may be returned as reux to the top of the column 24 by means of a valved line l2 connecting line 3l with the top of the column 24. Instead of returning reflux to the -top of the column 24 a refrigerating coil may be used in the top of the column to provide the necessary amount of reiiuxing.

The olefin mixture containing the compoundsy of higher boiling point than ethylene, are collected'in the base of the column 24 and withdrawn through a valved line 34, and introduced into the midportion of a second rectifying column 3i. In this column the conditions are so regulated that the propyiene is fractionated out and driven overhead through a vapor line 38, and it may be used in vapor form or condensed in a condenser 4I from which the liquid condensate is conducted by a line 42 for further treatment or to storage. Any portion of this condensate may be introduced as reiiux into the column 36 through a valved line 44 connecting with the line 42.

The higher boiling olefin mixture still remaining in vcolumn $6 and which gravitates to the bottom thereof, is withdrawn under reduced pressure through a valved line 4l and passed into a third rectifying column 4l. In this column the pressure and temperature conditions are controlled so as to fractionate out the butylenes, or a butylene fraction, which is driven overhead through a vapor line 50 and condensed in a condenser 52. The vapors in the line 50 (and line Il) of course may be used directly without subjecting them to condensation. The liquid butylene product from condenser 52 is conducted for use or storage through a valved line 54 and any desired part of this may be used for reflux in the column 4I by passing it through a valved connecting line 58. Instead of returning redux condensate to any one of these fractionating used to produce the desired amoimt of reflux in the top of the column, and heating coils may be used in the base of each column.

'I'he remaining product which gravitates to the bottom of the column 48 may comprise substantially only the amylenes in the particular example mentioned above, and this material is withdrawn to storage or for use through a valved line 58. The product withdrawn from the bottom of column 48 may be further fractionated if found desirable, and accordingly any number of additional rectifying columns may be employed without departing from the spirit and scope of the present invention.

If the proportion of some of the oleilnic compounds is comparatively large, or when the boiling points of the products are quite close together, it is often important to have a careful fractionation of the products in order to secure substantially pure fractions or compounds. In case it is desirable to carry out a fractionation to get a more complete separation of the individual oleiins than can be obtained with the ordinary bubble cap distillation, then a concentration of product in a bubble column having a boiling point slightly higher than the boiling point of the product to be recovered may be built up in the fractionating columns in order to assist in the fractionation. To build up the concentration of the propylene, for example, in column 24, a portion of the product may be taken from the line 42 through a line 60 and transferred by means of a pump mounted therein into the upper midportion of the column 24. By this means the concentration of the propylene in the column 24 may be built up to an unusual extent in order to assist in carefully fractionating out all of the ethylene passing into the column 24.

To assist in removing all of the propylene by means of the fractionating column 86, a portion of the product may be removed from the line 64 through aline 62 and forced by means of a pump mounted therein into the upper midportion of the column 36. By this means one or more butylene compounds may be returned to the column 88 to assist in driving the propylene overhead. 'I'he separation of the butylene by means of the column 48 may be assisted by using a slightly higher boiling product from an outside source which is forced through a line 64 into the upper midportion of the column 48. If necessary a small column may be connected with the line 58 by which the product passing through the line 88 may be fractionated and one of the lighter fractions returned to the midportion of column 48.

In the specific example considered above, for the extraction of oleiins from cracking still gases. a pressure of approximately 150 lbs. per square inch may be maintained in absorber 6, about 250 lbs. per square inch in column 24, about -190 lbs. per square inch in column 86, and about 50 lbs. per square inch in column 48. With the use of these pressures, the temperatures in the rectifying columns will be controlled to ehect the de sired fractional separation as outlined above.

The individual oleins or fractions produced by the rectification operations in the columns 24, 36 and 48 may be polymerlzed under heat and pressure for the production of higher boiling products particularly those boiling in the motor fuel range. For example, the ethylene conducted through the line 30 may be passed at a pressure of from 400 to '100 lbs. per square inch by means of a pump 66 and a line 68 to a polymerizing coil mounted in a pipe still furnace, In

passing through the coil 10, the ethylene may be polymcrimd by applying a high"temperature of from 950' to 1350 F., depending upon the reaction time, after which the products are dis- 5 charged through a transfer line 12 into the upper portion of an enlarged reaction chamber 14 in which the highly heated products are permitted to react for an extended period of time to produce polymerization products. 'I'he temperature l0 and rate of flow of vapors through the reaction chamber 14 are controlled so that the reaction is completed by the time the vapors reach the outlet from the chamber. At this point the vapors are rapidly cooled by spraying a quench 15 fluid such as a light oil distillate or'water into the vapors from a valved line 16. The resulting cooled vapors are thereafter conducted for subsequent fractionation through a valved line 16.

Ihe propylene produced by the fractionating in column 88 may likewise be subjected to thermal polymerization by conducting the recovered propylene 0r propylene fraction from the line 42 through a pump 18 at a pressure of about 350- 600 lbs. per square inch, through a line 80, by which the propylene is conducted to a polymerizing coil 82, mounted in a pipe still furnace. 'I'he propylene passing through the coil 82 is preferably heated to a temperature of from 900 to 1250 F., depending on the reaction time, and then discharged through a transfer line 84, into an enlarged vertical reaction chamber 88, where the propylene or products discharged from the coil 82 are permitted to polymerize while slowly passing downwardly through the chamber. The hot reaction products are quickly cooled by a fluid injected through a valved line 81 in the same manner as for chamber 14. The resulting polymerization. products, together with unconverted propylene, are then discharged from the chamber 88 through a valved line 88, for subsequent fractionation.

The "butylene, butylene fraction, or butylenes, recovered from the torwer' 48 in the line 64 .may be subjected to thermal polymerization in a. manner similar to that described above in connection with the propylene and ethylene by forcing the material in the line 64 at a pressure of from 300 to 600 lbs. per square inch, by means of a pump 88 and a line 82, inte a polymerization coil 84 mounted in a pipe still furnace. In this coil the fraction from the tower 48 is subjected to polymerizing temperatures of the order of 850 to 1100 F., depending upon the reaction time, and then conducted through a transfer line 96 into a reaction chamber 98 wherein the highly heated products are permitted to react for an extended period of time suiilcient to produce liquid products of higher boiling point than butylene. The resulting reaction products are quenched like those in chamber 14 by introducing a cooling fluid through a valved line 89, and then discharged through a valved line |08 for subsequent fractionation.

The highly heated conversion products conducted from the polymerization operations by lines 18, 88 and |88 may be separately fractionated if desired, but they are conveniently handled by combining them in a vapor line |02 in which they preferably have a temperature of from 600 to 700 F. The resulting mixture is conducted into a separating chamber |06 Where any liquefied products are permitted to separate out for removal through a valved line |08. The

remaining vapors preferably at a temperature of 75 about 650 F. are conducted into a fractionating tower III, above the chamber III, and subjected to rectification to condense all constituents of higher boiling point than those desired in the gasoline or motor fuel product. This rectification may be aided by a cooling coil in the upper part of the tower III.

The vapors and gases remaining uncondensed in the tower III are conducted through a vapor line II2, condensed in a condenser, and .the resulting condensate and uncondensed gases passed to a receiver III. The receiver II4 is maintained under a superatmospheric pressure of from 225 to 250 lbs per square inch, which pressure is also maintained in tower III from the higher pressures inthe reaction chambers. The gas separated out therefore in receiver ||4 will be substantially "dry" and the condensate will contain considerable proportions of C4, C: and Cz hydrocarbons. This material is stabilized by conducting it from the receiver III through a valved line III into a stabilizer III operated to produce a gasoline of desired vapor pressure and eliminate overhead the Cz, C: and undesired proportions of the C4 hydrocarbons.

The product withdrawn from rectifying tower 4I through line II is a very desirable motor fuel constituent and is therefore preferably passed through a valved line III by means of a pump mounted therein and introduced into the upper mldportion of the stabilizer ||I to aid in the rectification therein and to blend the product with the gasoline normally produced by the stabilizer. The desired bottom temperature in the stabilizer may be maintained by heat derived from the vapors in line II2 by using a heat exchanger as illustrated in the drawings. The gasoline product produced in the stabilizer is withdrawn through a valved line |2I.

The overhead vapors and gases removed from the stabilizer III are passed through a vapor line |22 and a condenser to produce sufilcient condensate for refluxlng the upper part of the stabilizer, the resulting condensate and uncondensed gases being directed to a receiver |24, from which the reflux liquid is introduced into the stabilizer through a valved line I2I. Only sufilcient of the vapors passing through the line |22 is condensed to provide the required reflux ratio in the stabilizer III. The gases in the receiver |24 are removed through a line I2I and passed into the line I leading to the absorber I. The gases from the receiver III may also be sent to the absorber I by means of a valved line III which discharges into the line I2I. A pressure of about I1I lbs. per square inch is maintained in the receiver |24 and stabilizer I II.

The present invention may advantageously inintroduoedintothesamecoil. Theintroduction -oftheoilintothemidportionofthecoilispreferred because it provid a convenient method of instantaneously vaporizing the oil so that it is crackedintheremainderofthecoil, andthereaction chamber associated therewith, while it is inthe vapor phase. Where the coils 1I, I2 and I4 are used for the combined polymerization of olefins and the cracking of hydrocarbon oils, the

temperatures of the products discharged from the coils should not be raised above 1100 P. Thismaytosomeextentdecrease the proportion of olefin polymerization obtained, from that secured for example at higher temperatures, particularly where ethylene and propylene are involved. However, the combined treatment oi hydrocarbon oil and olefins provides an. operation in which the vapor pressureof the desired unsaturatedhydrocarbonsmaybebuiltupinthe product passing through the cracking coil in order to promote the desired reaction, and thus produce the product desired. For example, if it `IsdesiredtoincreasetheconcentrationofbenzoL clude the simultaneous polymerization of oleiln hydrocarbons as described above, along with the cracking of hydrocarbon oils. As an example, the hydrocarbon oil such as gas oil may be introduced into the apparatus shown in Fig. l through a line II2 and forced ata suitably high pressure by means of -a pump mounted therein into the coils 1I, I2 and II. The oil to be cracked in each of these coils may be introduced into the midportion of each coil, at a point where the gas has reached a relatively high temperature, through suitable valved branch lines III, III and III respectively. If desired, the oil may be introduced to the inlet of each of the respective furnaces through valved branch lines |4I, |42 and |44, or at both points. The proportion of oil in' troduced into any one of the coils 1I, I2 or II, is preferably not greater than the weight of gas this canbeaccomplished byincreasingthepercentage-of higher boiling oleilns. 0n the other hand, alkylated benzol may be formed by controlling the percentage composition of the ethylene, propylene or butylenes .passed to the respective coils 1I, I2 and I4.

The reflux condensate formed in the towerI II which may contain gas-oil and some lighter constituents, is preferably withdrawn through a valved line III into the line II2 and sent to the conversion coils 1I, I2 and I4. The cooling fluid introduced through the lines 1I, I1 and II preferably is a hydrocarbon oil which will be sul.4

stantially completely vaporized in the lower portion of the reaction chambers while it produces the desired cooling. Gases containing olei'lns may alsobeusedasacoolingmediuminthelines 1I, I1 and II, since they eventually would reach the absorber I by way of lines I2I and III.

Instead of polymerizing the individual oleilnsor fractions produced by the columns 24, II and 4I, by heat and pressure :(thermal polymerization) or by combining their polymerization with the cracking or conversion hydrocarbon oils, as described in connection with Fig. l of the drawings, the olenic compounds or individual frac-v tions produced by the columns 24, II and 4I. may be polymerized with a suitable catalyst by utlizing the apparatus shown in Fig. 2 of the drawings. Inthisiigureoi'thedrawings,the selective absorption, recovery and fractionation of the oleiln hydrocarbons to be polymerized Is identical with that described in connection with Fig. 1, and the apparatus elements involved In these steps are designated by the same reference characters.

Therefore, referring to Fig. 2 ofthe drawings, the ethylene recovered in the line II is passed by means of pump II through a line III and a heating coil II2 mounted in a pipe still furnace. In this coil, the ethylene is preferably heated under a pressure of about 500 to '150 lbs. per square inch to a discharge temperature of from 375 to 800 F., after which it is passed into a distributing line III from which it is conducted, preferably with 0.1 to 0.5 of oxygen or water as an accelerator, through one of three alternate valved lines III, into the upper portion of one of three alternate catalyst polymerization chambers III. Each chamber is preferably filled with a catalytic material such as alumina or phosphoric acid deposited on some porous carrier or inti'- mately mixed with such porous carrier which may be cast into desired relatively small shapes. 'I'he ethylene is preferably passed through two of the chambers in series while the other catalyst chamber is cut out of the system and the catalyst revivied. The ethylene therefore introduced into the upper portion of one of the chambers |58 passes downwardly through the catalyst therein, through two of three alternative valved lines |80, into the bottom of one of the remaining chambers, and upwardly through the body of catalyst therein. The ethylene in passing through the catalyst in two of the chambers is preferably maintained at a pressure of approximately 500 lbs. per square inch and undergoes considerable polymerization to hydrocarbons which are liquid at normal temperatures. The resulting products are discharged from the last of the two contact chambers through one of three alternate valved lines !82, into a valved collecting line |64.

The catalyst chamber |58 which is cut out of the circuit for revivication of the catalyst is isolated by closing the valves in lines |58, |80 and |62 leading thereto. Before closing the valve |82 the products which would normally remain in the chamber |58 upon closing valves |58 and |80 may be replaced and forced out into the line |64, or vented to suitable receiving apparatus through a valved vent line |66. In any case, when the isolated chamber is ready for reviviilcation of the catalyst the vent line |66 is opened and hot products of combustion for example from the pipe still furnace is forced through a line |68 by means of a pump or blower (B) mounted therein, through an appropriate valved branch line and used to revivify the catalyst along with a suitable proportion of air introduced through a valved line |12. After the catalyst in the isolated chamber has been revivifled. it is purged to remove oxygen and then the valves in lines I 66 and |10 are closed and the chamber put back into the polymerization cycle, preferably as the last in series of the two catalytic chambers being used to polymerize the ethylene. The three chambers |58 may therefore be used so that two chambers are in the cycle, and while the other chamber is cut out of the system for reviviflcation of the catalyst therein 'Ihe propylene fraction removed from the tower 38 through the line 42 is forced by means of pump 18 at a pressure of from 400 to 600 lbs. per square inch through a line |14 and a heating coil |16 mounted in a pipe still furnace. and therein heated to a temperature of from 350 to 700 F. The resulting hot propylene is conducted through a distributing line |18, preferably with from 0.1 to 0.5% of oxygen or Water as an accelerator, and subjected to catalytic polymerization in catalyst chambers 80 containing, for example, zinc chloride or phosphoric acid on a carrier, by a procedure identical with that described in connection with ethylene and chambers |58. 'Ihe various connecting lines for the alternate operation of chambers |80 are designated by the same numerals as those applied to the corresponding lines of chambers |58. 'I'he products resulting from the polymerization of the propylene fraction are discharged into a valved collecting line |82 for subsequent fractionation. A pressure of approximately 350 to 500 lbs. per square inch, is

preferably maintained in the catalyst chambers |80 during the polymerizing operation.

'I'he butylene compound or fraction recovered overhead from the tower 48 and removed through the line 64, is conducted under a pressure of from 375 to 500 lbs. per square inch by means of pump 90 and passed through a line |84 and a heating coil |88 mounted in a pipe still furnace, and therein heated to a temperature of from 265 to 400 F. The resulting heated butylene or fraction is passed through a. distributor line |88, along with 0.1 to 0.5% of oxygen or water, to the upper portion of one` of three catalyst chambers |90. These chambers preferably contain orthophosphoric acid on diatomaceous earth, are operated in exactly the same manner as the chambers |58 and all of the connecting lines are designated by the same reference numerals as those connected with chambers |58. 'I'he polymerization product resulting from the polymerization of the butylene in the chambers |90 is collected in a valved line |92 for subsequent fractionation.

'I'he products produced by the polymerizing operations carried out in chambers |58, and 90, are passed through lines |84, |82 and |92, into a vapor-collecting line |94, and subjected to fractionation in equipment identical with that shown and described in connection with Fig. 1 of the drawings, by the passage of the vapors from the line |94 into the separating chamber |06 and the subsequent apparatus elements shown.

In carrying out the polymerization of the olefins in chambers |58, |80 and |90, there is an exothermic temperature rise above that of the temperature of the gas introduced. For ethylene the temperature rise in the rst chamber is about 110 F., and in the second chamber about 25 F, For propylene, the corresponding temperature rises are slightly lower, that is, about 100 F. for the first chamber, and about 20 F. for the second chamber. The butylene fraction produces an exothermic temperature rise of about in the iirst chamber and about 15 in the second chamber.

Various other catalysts may be employed in the chambers |58, |80 and |90, such for example as aluminum chloride, zinc chloride. phosphoric acid, silica gel, iron phosphates and alumina. Other aluminum halides may be used, for example, aluminum bromide is a very powerful catalyst. Any of these catalysts may be deposited on a carrier material.

Various modifications may be made in the operation of the apparatus shown in Fig. 2, and in the polymerization steps.v For example, a certain proportion of propylene may be subjected to polymerization with the butylene, but ordinarily the propylene content of the charging stock should not exceed about one third of the butylenes. Similarly, a small percentage such as 10% of ethylene, may be included in the propylene stock for the coil |16. 'I'hese small percentages of lower oleiins may be polymerized with higher olens, but as a general rule, as mentioned above, entirely different conditions must be maintained for effective polymerization of the various olens. The operations carried out in chambers |58, |80 and |90, never completely polymerize the entire charging stock, so that there is always certain unreacted gases as well as the production of other gases both saturated and unsaturated in the products from these chambers. These materials are recovered as described in detail in connection with the apparatus shown in Fig. 1, and sent back to the absorber 6 for segregation of the olens which are recycled in the process.

The importance of the process of the present invention may be readily appreciated from the fact that a mixture of olefins cannot be successfully converted by polymerization into high antiknock gasoline without destroying a large part of the olefins. The temperature and pressure conditions for the thermal polymerization of ethylene for example, are entirely unsuited for the thermal polymerization of the butylenes. However. according to the present invention, these various olens may be eflectively separated from the paraiilns, separately recovered and utilised individually in a very economical manner. The separation of the oleiins from the paraiilns is very important because of the fact that the parailins are not polymerised under the conditions of the process, and tend to enter into other reactions and act as diluents. The paramns in gas mixtures therefore actually hinder the proper utilisation of the olenns contained in such mixtures.

By carefully fractionating and separating the diiferent oleiinic products these products may be placed in suitable -condition so that they may be readily nitrated or suifated to form their corresponding hydrates, nitrates and sulfates. and these products then treated to make alcohols and esters. By carefully fractionating the products the desired end product can be formed directlyl and a very substantial saving made in the final reiining of the product. Where a mixture of different oleiins is treated with acids, the reaction cannot be as accurately controlled as where single products are converted into esters and slcohols. Furthermore, the percentage conversion of the products may be very much higher and thus avoid loss due to secondary reactions or the formation of constant boiling mixtures or interaction between various intermediate products.

From the foregoing description, it is readily apparent that various modincations may be made in the process of the present invention without departing from the spirit of the invention.

Having thus described the invention in its preferred form, what is claimed as new is:

l. In the production of motor fuels in which an oleiin gas is polymerined into normally liquid ,constituents boiling within the gasoline range, the improvement which comprises passing a gaseous mixture containing olefinic Cs, C: and Cl hydrocarbons in intimate contact coimtercurrent to a selective solvent for the olefin hydrocarbons of said mixture comprising a member of the group consisting of alkyl ethers and dichlorides of alkyl ethers in which each alkyl radical contains four or more carbon atoms, selectively absorbing the oleilns from said gaseous mixture into said solvent, passing the solvent containing the absorbed oleiins into a still and .separating the oleiins from the solvent to produce a vapor mixture containing Cz, Ca, and C4 oleilnic hydrocarbons which is substantially free of paraiiin hydrocarbons, subjecting the mixture of olefin vapors from said still to 'a series of high pressure rectifying operations to produce separate `oleiin fractions containing respectively essentially only Cz, C: and C4 oleiins, separately subjecting said fractions to polymerization in individual polymerizing sones maintained under controlled conditions of temperature and pressure particularly adapted to polymerize the separate fractions into hydrocarbons of higher 'molecular weight, recovering the normally liquid polymers produced from said fractions and recycling the unrcacted olens back through the absorption steps of the process.

2. The process of making organic compounds contacting a gaseous mixture containing hydrogen, paraiiinic hydrocarbons. and Cs, Cs and C4 oleiinic hydrocarbons with a selective solvent adapted to selectively absorb the olennic hydrocarbons from the gaseous mixture, separating the absorbed olefin hydrocarbons from the selective solvent as a mixture containing Ca, C: and C4 olefins which is substantially free of parafiin hydrocarbons, passing the resulting oleiin mixi0 ture into a first rectifying zone and therein producing an overhead oleiin fraction comprising substantially only ethylene, passing the remainder of the olefin mixture from said iirst rectifying zone to a second rectifying zone in 1s which an overhead fraction comprising essentially only propylene is produced, rectifying the remainder of the olenn mixture in a third rectifying sone and producing an overhead fraction comprised essentially only of C4 olefins, separatezo 1y subjecting said overhead olefin fractions from said rectifying sones to separate conversion operations under controlled conditions of temperature and pressure particularly adapted for the conversion of each olefin fraction into organic compounds of higher molecular weight, recovering the organic compounds produced by said conversion operations and recycling the unreacted normally gaseous hydrocarbons from each of said conversion operations back through the absorption steps of the process for retreatment.

3. The process of making organic compounds from olefin hydrocarbon gases. which comprises 'contacting a gaseous mixture containing hydrogen,paramnic hydrocarbonsandCs,C:|andC4 oleilnic hydrocarbons with a selective absorbent solvent adapted to selectively absorb the olefin hydrocarbons from the mixture and thereby separate them from the remaining constituents of the mixture. carrying out said contacting opera- 40 tion under controlled conditions of temperature and pressure particularly adapted for eifecting said absorption, separating the absorbed oleflns asamixture fromtheselectivesolventpassing the separated olefin mixturethrough a series oi fractionating columns and fractionating out indivldual olefin fractions comprised respectively of essentiallyonlycsandCsolennichydrocarbons, passing said oleiin fractions .to separate polymerizing sones, each including a heating coil. wherein each fraction is polymerised to produce organic compounds of higher molecular weight under conditions particularly adapted for the polymerization of each individual fraction, introducing petroleum oil at an intermediate point into the'coil of each zone and cracking it simultaneouslywiththeoleiinsubiectedtopolymcrisation therein, collecting the normally condensible products resulting from said separate cracking coil operations and recycling the gaseous hydrocarbons from said cracking coil operations back through the absorption step of the process for retreatment.

4. The process of making organic compounds condensible under normal conditions of temperature and pressure from olefinic hydrocarbon gases, which comprises intimately contacting a gaseous mixture containing hydrogen. paraiilnic hydrocarbonaandCaCaandCsolefiniehydmcarbons with a selective solvent in a contact lone. said solvent being adapted to selectively absorb the olefinic hydrocarbons from the gaseous mixture and thereby separate the olefins from the remaining constituents of the mixture. separatingtheahsorbedoleiinsfromthesolventasa from oleiinic hydrocarbon gases, which comprises mixture which is substantiallyI free of parailln and pressure particularly adapted for effecting said absorption, separating the absorbed olens from the-selective solvent, passing the separated olenn mixture through a series of fractionating columns and iractionating out individual olefin fractions comprised respectively of essentially only C2, Cb andv C4 olefinic hydrocarbons, passing said oleiln fractions to separate polymerizing zones, each including a heating coil, wherein each fraction is polymerizcd to produce organic compounds of higher molecular weight under tion and recycling for retreatment in the contact zone of the process any gaseous hydrocarbons remaining from the products removed from said polymerizing zones.

5. The process of making organic compounds 'from olefin hydrocarbon gases, which comprises contacting a gaseous mixture containing hydrogen, paraifinic hydrocarbons and Cn, Cs and C4 oleilnic hydrocarbons with a selective absorbent solvent adapted to selectively absorb the olefin hydrocarbons from the mixture and thereby separate them from the remaining constituents of the mixture, carrying out said contacting operation under controlled conditions of temperature conditions particularly adapted for the polymerization of each individual fraction, passing the conversion products from said zones to a common fractionating tower and therein fractionating out constituents'of higher boiling point than gasoline as reflux condensate, introducing portions of said reiux-condensate into the coil of each polymerizing zone and cracking it simultaneously with the olens subjected to polymerization therein, fractionating the remaining vapors including the gasoline constituents from said fractionating tower to condense the normally condensible products including the gasoline boiling range constituents, and recycling the gaseous hydrocarbons from said fractionating operations back through the absorption step of the process for retreatment.

' EDMUND G. BORDEN. 

